JPS6157863B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aromatic polyamide compositions having improved dyeability and excellent heat resistance. Fully aromatic polyamides are known to be suitable for a wide range of applications. It has a higher softening point and melting point than aliphatic polyamide, and has excellent heat resistance such as strength retention, shape stability, and thermal decomposition properties at high temperatures, flame resistance, and flame retardancy, as well as chemical resistance. Woven fibers with highly desirable physical and chemical properties such as electrical properties, mechanical properties such as strength and Young's modulus, and are heat resistant, flame retardant, flame retardant, and woven fibers with high strength and high Young's modulus. Suitable for applications such as , films, and molding materials. However, when this wholly aromatic polyamide is used as a woven fiber, it has the drawback that it cannot be easily dyed by ordinary dyeing methods due to its highly oriented and crystalline nature. Therefore, for applications that require its excellent properties, uncolored wholly aromatic polyamide fibers are used as electrical insulating materials for motors, transformers, etc., industrial applications such as filter bags, heating tubes, and other aesthetic applications. Although widely accepted in textiles where no element is required, it is highly desirable to provide easily dyeable aromatic polyamide fibers for textile textiles where trendy colors are considered important. . The object of the present invention is to improve the poor dyeability of aromatic polyamides while maintaining their excellent properties as much as possible. Conventionally, one of the methods for improving the dyeability of aromatic polyamides is to use functional groups that have an affinity for dyes, such as
A method for obtaining fibers from polyamide copolymers having sulfone groups, tertiary amino groups, or quaternary ammonium groups in the polymer chain (Japanese Patent Publication No. 45-34776,
52-43930) and methods for obtaining fibers from compositions comprising such polyamide copolymers and wholly aromatic polyamides are known. (Tokuko Showa 49-32658,
Tokuko Sho 49-32659, Tokuko Sho 49-33594, Tokuko Sho 50-
8104) However, although the fibers obtained by these methods have improved dyeability, they are significantly inferior in thermal properties, which are most required for the use of this type of fiber. In order to improve the above-mentioned drawbacks, the present inventor aimed to improve the poor dyeability of wholly aromatic polyamide fibers to a practical level, and to achieve the excellent twisting properties of wholly aromatic polyamide fibers. As a result of intensive research into compositions that provide fibers that retain
We have arrived at the present invention. The composition of the present invention is a polyamide (B) consisting of polymetaphenylene isophthalamide (A) and a phenylenediamine having at least one alkyl group having 1 to 4 carbon atoms in the benzene nucleus, an aromatic diamine, and an aromatic dicarboxylic acid. The composition of
The former (A) is preferably 95 to 50% by weight, and the latter (B) is preferably 5 to 50% by weight. In compositions in which the proportion of the latter (B) is less than 5% by weight, the fibers obtained therefrom may be heated at 300°C.
Even if the thermal properties such as the heat shrinkage rate are satisfied, the dyeability is significantly reduced. Also, the ratio of the latter (B) is
Even if the dyeing properties of the fiber obtained from a composition larger than 50% by weight are satisfactory, the thermal properties such as the heat shrinkage rate at 300° C. are significantly reduced. Further, although the preferable proportion of the composition varies depending on the composition of the latter polyamide (B), the proportion of the latter (B) is generally 5 to 50% by weight, most preferably 10 to 30% by weight. Polyamide which is one of the components of the composition of the invention
(B) is 35 to 100 mol% of phenylenediamine having at least one alkyl group in the benzene nucleus;
It consists of an amine component consisting of 65 to 0 mol% of aromatic diamine and an acid component consisting of aromatic dicarboxylic acid. Phenylene diamine, which is one of the amine components of the polyamide (B) and has at least one alkyl group in the benzene nucleus, but has 1 to 4 carbon atoms, is O-
phenylenediamine, m-phenylenediamine,
P-phenylenediamine has at least one alkyl substituent on the benzene nucleus. Among the phenylene diamines, m-phenylene diamine and P-phenylene diamine are preferred, and m-phenylene diamine is more preferred. Further, the alkyl substituent can have one or more and up to four, and the positions of the substituents can be arbitrarily selected.
When it has two or more alkyl substituents, the number of carbon atoms in the substituents may be the same or different. The number of carbon atoms in the alkyl substituent is suitably 1 to 4. Generally, it is preferable that the number of alkyl substituents and the number of carbon atoms in the alkyl substituents are small. If the amount of these diamines is too large, the polymerizability of the diamine generally tends to deteriorate, and the solubility of the polyamide (B) obtained therefrom also tends to decrease, and furthermore, the properties such as heat resistance of the composition of the present invention tend to deteriorate. There is also a tendency to decrease. Examples of the diamine include 2,5-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 4-ethyl-metaphenylenediamine, 2-ethylmetaphenylenediamine,
-isopropyl-metaphenylenediamine, 4-
n-Butyl metaphenylene diamine, 2-ethyl para phenylene diamine, 2,6-dimethyl- meta phenylene diamine, 4,6-dimethyl meta phenylene diamine, 2,5-dimethyl para phenylene diamine, 2. Examples include 3,5,6-tetramethylparaphenylenediamine and mixtures thereof. Preferred examples include 2,5-diaminotoluene, 2,4-diaminotoluene, and 2-diaminotoluene.
6-diaminotoluene, 4-ethylmetaphenylenediamine, 2-ethylmetaphenylenediamine, 4-isopropylmetaphenylenediamine,
2,5-dimethylparaphenylenediamine, 4.
Among 6-dimethylparaphenylenediamine and mixtures thereof, the most preferred are 2,4-diaminotoluene, 2,6-diaminotoluene, and mixtures thereof. The aromatic diamine which is another amine component of the polyamide (B) includes phenylene diamine,
Examples include naphthylene diamine, biphenylene diamine, diphenylthioether diamine, diphenyl ether diamine, diphenylmethane diamine, and diphenyl sulfone diamine. Specific examples of such aromatic diamines include paraphenylenediamine, metaphenylenediamine, 2.
4 diaminochlorobenzene, 2,6 naphthylene diamine, 4,4'-biphenylene diamine, 4,
Examples include 4'-diaminodiphenyl ether, 3,4'diaminodiphenyl ether, 4,4'diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'diaminodiphenyl ether. More preferred is metaphenylenediamine. Further, examples of the aromatic dicarboxylic acid which is the acid component of the polyamide (B) include phenylene dicarboxylic acid, naphthalene dicarboxylic acid, and mixtures thereof. The hydrogen atom of the benzene nucleus of these aromatic dicarboxylic acids may be replaced by a substituent that does not react with the acid halide group or amino group. Such substituents include halogen, lower alkyl, phenyl, carbalkoxy, nitro, thioalkyl, and the like. Specific examples of such aromatic dicarboxylic acids include terephthalic acid, monochloroterephthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid, methylterephthalic acid, isophthalic acid, 2.6
- such as naphthalenedicarboxylic acid. Preferably terephthalic acid, isophthalic acid, 2.
6-naphthalene dicarboxylic acid, more preferably terephthalic acid or isophthalic acid. The amine component of the polyamide (B) preferably has a ratio of 40 to 100 mol % of phenylene diamine having at least one alkyl group having 1 to 4 carbon atoms in the benzene nucleus and 60 to 60 mol % of aromatic diamine. When the amount of phenylenediamine having at least one alkyl group having 1 to 4 carbon atoms in the benzene nucleus is less than 40 mol %, the dyeability is significantly reduced. Benzene nucleus has 1 carbon number
The proportion of phenylenediamine having at least one alkyl group of ~4 varies depending on the type and proportion of other aromatic diamines and aromatic dicarboxylic acids constituting the polyamide (B), but is 50 to 100 moles. % is more preferably 75 to 100 mol%
It is. Logarithmic viscosity I as a guideline for the degree of polymerization of a polymer,
Display using V. I and V are determined from the following formula by measuring a solution of a polymer dissolved in concentrated sulfuric acid at 30°C. I, V, = 1 nηr/C C = polymer concentration polymer g/concentrated sulfuric acid dl I, V of the polyamide (B) are preferably 0.1 or more. The polyamide (B) can be obtained by conventionally known methods for synthesizing polyamides, such as solution polymerization, interfacial polymerization, melt polymerization, and solid phase polymerization. Preferred methods are solution polymerization and interfacial polymerization. Further, the aromatic dicarboxylic acid constituting the polyamide is used in the polymerization as a dicarboxylic acid or as an amide-forming derivative such as an ester or an acid halide. Preferably, it is an acid halide, more preferably an acid chloride. Polymetaphenylene isophthalamide (A), which is one component of the composition of the present invention, may be copolymerized with another diamine or dicarboxylic acid as a copolymerization component of up to 10 mol% of the total diamine and dicarboxylic acid components. . Furthermore, the composition of the present invention may contain various polymeric additives such as light stabilizers and flame retardants for the purpose of improving its properties. Any method may be used to produce the composition of the present invention, but a solvent such as N.
A necessary amount is mixed and dissolved in a basic amide solvent such as N'dimethylformamide, N.N'dimethylacetamide, or N-methyl-2-pyrrolidone to form a molding solution, and the composition is molded into fibers, films, fibrids, etc. It is preferable to obtain crystals. Mixing and dissolving may also be done by any method. Any method may be used, such as mixing mutually dissolved polymer solutions, dissolving and mixing one polymer in one solution, or mixing polymers in powder form and then dissolving them at the same time. The mixed solution can also be obtained by mixing and dissolving in a solution obtained from solution polymerization, or by previously dissolving one of the polymers in a polymerization solvent before solution polymerization. The method for producing fibers of the composition of the present invention includes 95 to 50% by weight of polymetaphenylene isophthalamide (A) and 40 to 100% of phenylenediamine having at least one alkyl substituent having 1 to 4 carbon atoms on the benzene nucleus. mol%, 60 to 0 mol% of aromatic diamine as an amine component and 5 to 50% by weight of polyamide (B) having an aromatic dicarboxylic acid as an acid component is extruded to form fibers, and the fibers are also formed. 1.5~ of extrusion length with
It consists of stretching 5.0 times and then subjecting the fiber to tension heat treatment or hot stretching at a temperature of 280°C or higher. The step of extruding the fibers to form fibers may be carried out by any of dry spinning, wet spinning, or semi-dry and semi-wet spinning using a solution of the composition, and it is preferable to carry out a water washing step before stretching. . The fiber is then 1.5 to 5.0 of the original extrusion length.
This stretching is preferably carried out in water or an aqueous solution containing a solvent or salts at room temperature to 100° C., or in steam. Furthermore, after drying, the fiber is subjected to tension heat treatment or hot stretching at a temperature of 280° C. or higher. In many cases, hot stretching is preferable here;
The preferable hot stretching ratio is 1.05 to 5.00 times. The composition of the present invention can be prepared according to the composition ratio of phenylenediamine having at least one alkyl group having 1 to 4 carbon atoms in the benzene nucleus in the polyamide (B) and the ratio of the polyamide (B) in the composition. By appropriately selecting the manufacturing conditions described in 1., it is possible to form fibers with improved dyeability and a preferable heat shrinkage rate of 300°C. Thermal shrinkage rate at 300°C was taken as a measure of the heat resistance of fibers. The value of the heat shrinkage rate in the examples and comparative examples is defined by the following formula by measuring a certain length (l ₀ ) of the fiber and measuring the length (l) after relaxing treatment for 30 minutes in an atmosphere of 300 ° C. It is. Thermal shrinkage rate at 300°C (S ₃₀₀ ) = l ₀ - l/l ₀ × 100 (%) In addition, in order to show the difference in dyeability of fibers, after dyeing under the following dyeing conditions, wash thoroughly with water, and The K/S of the dried fiber sample was measured by soaping at 80° C. for 30 minutes with an aqueous solution of 0.5 g of sodium dissolved in 300 ml of water, and the K/S values are described in the Examples and Comparative Examples. Fiber sample 10.0g Dye Supranol Blue 0.6g Ammonium sulfate 22.5g Acetic acid 6.0g Dyeing aid paraphenylphenol 2.0g Water 300ml Dyeing temperature and time 130℃ x 90 minutes K/S value is constant for well-opened fibers The reflectance (R) of light with a wavelength of 500 mμ was measured using a spectrophotometer by packing the amount into a cell of a certain size and using the following formula. K/S=(1-R) ² /2R The fibers made of the composition of the present invention are not limited to the above-mentioned acid dyes, but can also be practically used with dyes of other colors and various other dyes (such as cationic dyes). It has improved dyeability that allows it to be dyed to a certain level. Examples and comparative examples of the present invention will be described below. Example 1 A solution of 10.995 g of mixed toluylenediamine containing 2,4-diaminotoluene and 2,6-diaminotoluene in a ratio of 80:20 dissolved in 150 ml of tetrahydrofuran was dissolved in 18.273 g of terephthalic acid chloride.
was dissolved in 150 ml of tetrahydrofuran and slowly added dropwise to the solution cooled to 0° C. while stirring.
Subsequently, the slurry solution obtained here was added to an aqueous solution in which 13.4 g of anhydrous sodium carbonate was dissolved in 300 ml of water and cooled to 0° C. with vigorous stirring.
After 3 minutes, about 300 ml of water was added and after further stirring for 5 minutes, the polymer was taken, washed three times with about 500 ml of water each time, filtered and dried three times, and dried at 100° C. under reduced pressure. The obtained polymer had an IV of 1.45. A spinning solution was prepared by dissolving 22.0 g of the polymer thus obtained and 124.7 g of polymer powder of polymetaphenylene isophthalamide (IV1.80) in 552.0 g of N-methyl-2-pyrrolidone. Next, this spinning solution was coagulated by extruding it through a nozzle with a hole diameter of 0.08 mm and a number of holes of 100 at a speed of 4.0 m/m into an inorganic salt bath mainly composed of calcium chloride, and after washing with water, it was stretched 2.30 times in boiling water. Then 1.82 on a hot plate at 340℃
I stretched it twice and rolled it up with a winder. The fiber thus obtained has a strength of 4.3 g/d,
Elongation is 47%, heat shrinkage rate at 300℃ is 13.5%,
K/S was 10.7. Comparative Example 1 Polymetaphenylene isophthalamide (I.
V.1.80) 105g to 395g of N-methyl-2-pyrrolidone
A spinning solution was prepared by dissolving it in g. Subsequently, this spinning solution was coagulated by extruding it into an inorganic salt bath mainly composed of calcium chloride through a nozzle with a hole diameter of 0.08 mm and 100 holes at a speed of 4.0 m/m in the same manner as in Example 1, and after washing with water, it was coagulated in boiling water. It was stretched 2.30 times, then 1.80 times on a hot plate at 340°C, and wound up with a winder. The fiber thus obtained had a strength of 5.0 g/de, an elongation of 44%, and a
The heat shrinkage rate at ℃ was 50% and K/S was 0.9. Examples 2 to 5 A solution of mixed toluylene diamine (TDA) containing 2,4-diaminotoluene and 2,6-diaminotoluene in a ratio of 80:20 dissolved in 125 ml of tetrohydrofuran in the amount shown in Table 1, The amount of terephthalic acid chloride (TPC) or isophthalic acid chloride (IPC) shown in Table 1 was dissolved in 125 ml of tetrahydrofuran and slowly added dropwise to the solution cooled to 0° C. while stirring. Next, the slurry solution obtained here was added to 25.0 g of anhydrous sodium carbonate.
was dissolved in 250 ml of water and added to the aqueous solution cooled to 0° C. with vigorous stirring. After 3 minutes, about 300 ml of water was added and after further stirring for 5 minutes, the polymer was taken out, washed three times with about 500 ml of water each time, filtered three times, and dried at 100° C. under reduced pressure. The IV of the obtained polymer is listed in Table-1. A spinning solution was prepared by dissolving 4.0 g of the polymer thus obtained and 20.0 g of polymer powder of polymetaphenylene isophthalamide (IV1.80) in 80 ml of N-methyl-2-pyrrolidone. Next, this spinning solution was passed through a nozzle with a hole diameter of 0.08 mm and a number of holes of 40.
Coagulation was carried out by extrusion in an inorganic salt bath mainly composed of calcium chloride at 4.0 m/m, and after washing with water, the surface was immersed in boiling water.
Stretched to the magnification described in Table 1 (boiling water stretching ratio DR ₁ ), and then stretched on a hot plate at the temperature T (°C) described in Table 1.
The film was stretched to the ratio described in 1 (hot stretching ratio DR ₂ ) and wound up using a winder. The fibers thus obtained had the strength, elongation, shrinkage rate at 300°C, and K/S listed in Table 1. Examples 6-9 Same as Examples 2-5, except that benzoyl chloride (BC) or P
-Chlorbenzoyl chloride (CBC) and diamine together with aniline (AN) or P-
A polymer was synthesized by adding chloraniline (CAN) to tetrahydrofuran in the weight shown in Table 2. Using these polymers, yarn was produced in the same manner as in Examples 2 to 5 under the conditions listed in Table 2. The results are listed in Table-2.

【table】

[Table] Examples 10 to 14, Comparative Examples 2 to 4 Blend polymers were synthesized using the monomers and molar ratios listed in Table 3 in the same manner as Examples 2 to 5, and the blending ratio was 20 wt%. A spinning solution was prepared in the same manner as in 2 to 5, and the results of yarn spinning are shown in Table 3.

[Table] Example 15 and Comparative Example 5 A fiber obtained in exactly the same manner as in Example 1 (blending ratio 15.0%) is referred to as fiber sample A. Further, a fiber obtained in exactly the same manner as in Comparative Example 1 (blending ratio: 0%) is referred to as fiber sample B. The results of dyeing fiber samples A and B with various dyes in the same bath are shown. It is clear that the dyeability of the fibers from the compositions of the invention is excellent.

【table】

【table】

【table】

[Table] Examples 16 to 19 Mixed toluylene diamine in Example 1
A polyamide was synthesized in the same manner as in Example 1 using the diamines shown in the table below instead of 10.995g. Silk was produced in exactly the same manner as in Example 1 using the obtained polyamide and polymetaphenylene isophthalamide. The results are shown in the table.

【table】

Claims (1)

[Claims] 1 Polymetaphenylene isophthalamide (A) 95~
50% by weight, and an aromatic compound in which the amine component consists of phenylenediamine nuclearly substituted with at least one alkyl having 1 to 4 carbon atoms and another aromatic diamine, and the acid component consists of an aromatic dicarboxylic acid. An aromatic polyamide composition comprising 5 to 50% by weight of polyamide (B).